Azo compounds of the thiophanthraquinone series



Patented July 10, 1951 2,559,673

UNITED STATES PATENT OFFICE AZO DYES OF THE THIOPHANTHRA- QUINONE SERIES Herman E. Schroeder and Lorraine A. Ringrose, Wilmington, DeL, assignors to E. I. du Pont de Nemours & Company, Wilmington, DeL, a corporation of Delaware No Drawing. Application June 17, 1949, Serial No. 99,877

4 Claims. (Cl. 260157) 1 This invention relates to the preparation of Weaker than the azole types of the first mentioned new dyes of the thiophanthraquinone series, and. patent. more particularly to diazoles of the following gen- It is an object of the present invention to proeral formula: uce new and valuable dyes of the thiophanthrain which X stands for sulfur or oxygen and the quinone series which dye cotton and related Rs stand for radicals of the group consisting of fibers from the usual alkaline hydrosulfite vats thiophanthraquinone, anthraquinone and halo in desirable yellow shades and which exhibit imgen-substituted thiophanthraquinone and haloproved brightness, tinctorial strength and fastgen-substituted anthraquinone radicals, at least ness properties as compared to dyes of similar one R being a radical of the group consisting of shade now available. It is a more specific object the thiophanthraquinone radical and the haloof the invention to produce thiophanthraquinone gen-substituted thiophanthraquinone radical, V t dyes Which are 4'Z4"-substituted-azobithe thiophanthraquinone radicals in each case D e y mp nd Ca ry at ea t ne h obeing connected to the azole ring through its phanthraquinoneazole groupbenzene nucleus, The compounds of the present invention may It has been recognized fo many years that in beprepared frorn the azobiphenylcarbonylaminothe dyes of the anthraquinone series, those in the ihlorhanthmqwnonecarbonyl ,chlorlfles more yellow range are generally deficient in their fastpar tmular disclosed and clalmed m our ness properties, more particularly with regard to senal 7 filefi or even fastness to light, although in general the dyes date helewlth which have the folmula' of the anthraquinone vat dye class are considered I to have good fastness properties. Where yellow dyes have been found in the anthraquinone series H 0 0 WhlCh have good fastness properties, they are A I ll ll usually either dull or weak tinctorially, and. N N N therefore the various dyes in the anthraquinone s 7 fastness, brightness and tinctorlal strength of 31 231 23 5???gg ggi sfi i g ii yi g: the particular dyes available. In U. S. Patent U 4 2,175,803 a g p of Symmetrical dianthraqui group, which are further condensed with aminononediazoles, more particularly imidazoles, 1,2 (N) -thiazoles and 2,1(N) -oXazoles which con tain an azo group, are disclosed. These com- 40 pending application Serial No. 99,876, which have pounds dye vegetable fibers in yellowish shades the formula:

and are said to exhibit good fastness to chlorine in which at least one R is athiophanthraquinone and boiling soap solution, and, in many cases, to radical and the second R may be either the thiolight. It has been found, however, that these phanthraquinone radical or the anthraquinone dyes are deficient in wet fastness, particularly in 5 radical but in which both Rs carry a halogen kier boiling, and in their vat stability. In U. S. atom in a position ortho to the carbonylimino Patent 2,228,455 a series of dianthraquinonyllinkage. imides containing azo groups are disclosed which The new azole dyestuffs of this invention may have relatively good fastness properties, but these be prepared by the following processes:

dyes have been found to be dull and considerably as (a) Oxazole ring closure of the thiophanthraaminothiophanthraquinones or with 1 mol of the ortho mercapto (or hydroxy) aminothiophanthraquinone followed by 1 mol of the ortho-mercapto- (or hydroxy) aminoanthraquinone.

(d) The dithiazoles may also be prepared by sulfur fusion of the diimide chlorides which may in turn be prepared from the diimides of Formula II with phosphorous pentachloride in the manner described in British Patent 322,184: Two (2) parts of the diimide of Formula II is heated at 175 C. with 1 part of PC in parts of orthodichlorobenzene or nitrobenzene as solvent until a definite change occurs in crystal structure as observed by microscopic test. After about 4 to 5 hours the reaction is complete. The diimide chloride is filtered from the cooled reaction mass, washed with orthodichlorbenzene and acetone in turn and dried at 40 to 50 C. The dried product, 1 part, is heated with 2 parts of sulfur and 4 parts of naphthalene at 210 C. for about 8 to 10 hours or until no imide chloride remains.

The new dyes of this invention dye vegetable fibers in yellow shades from orange alkaline hydrosulfite vats. The dyeings exhibit unusually good light fastness and tinctorial strength for yellow vat dyes. They exhibit the outstanding advantage over that they are printing colors stronger shades than the corresponding dianthraquinone derivatives, are easier to vat, and, in general, show better alkali-fastness properties. The compounds of this invention which contain Z-thiophanthraquinone groups show greater advantage in printing behavior and in strength build-up than those carrying only the one thiophanthraquinone group. The presence of only one thiophanthraquinone radical in these new dye molecules, however, imparts to the dye a very marked improvement in printing behavior and in strength of color to render these new dyes of very practical importance as printing colors.

The following examples are given to illustrate the invention. The parts used are by weight.

Example 1 oope i j'OO *@Ojj 4 amino-5chlorothiophanthraquinone), 5 parts of soda ash, 5 parts of potassium acetate, 0.15 part of cuprous chloride and 0.08 part of copper acetate was heated at 2l0-215 C. for four hours. The charge was filtered at 60 C. and the cake was washed with nitrobenzene, alcohol, water and dried. The 4,4 -azobiphenyl-4 ,4 -bis [5,6 (N) thiophanthraquinone oxazole], as a bright ellow product which was acid pasted and bleached with alkaline hypochlorite by usual methods, is represented by the formula:

It dissolves in concentrated sulfuric acid to give an orange color and dyes vegetable fibers in yellow shades of excellent light-fastness and strength from an orange alkaline-hydrosulfite vat. It also gives strong yellow prints when applied in the usual manner.

Example 2 A mixture of parts of nitrobenzene, 10 parts of 4,4-azobiphenyl-4' -(6-carbony1amino- 5 chloroanthraquinone) 4' (2-carbonylarninol-chloroanthraquinone), 5 parts of potassium acetate, 2.5 parts of soda ash, 0.05 part. of cuprous chloride and 0.025 part of copper powder was refluxed (210-215 C.) for five hours. The charge was filtered at 60 C., and the cake was washed with nitrobenzene, alcohol and water and dried. The 4,4-azobiphenyl-l [5,6 (N) -thiophanthraquinone oxazole] -4= 1,2 (N) -anthraquinone oxazole], as a deep yellow-colored product which was purified through acid pasting and bleaching, is represented by the formula:

It dyes vegetable fibers in yellow shades of excellent light-fastness and tinctorial strength from an orange alkaline hydrosulfite vat.

Example 3 A mixture of parts of nitrobenzene, 4,4- azobiphenyl 4i" (6 carbonylamino-5-chlorothiophanthraquinone) -l"'-[1,2(N) anthraquinone thiazolel (prepared from 11 parts of a20- biphenyldicarbonyl chloride, 6.6 parts of 5'-chl0- ro6-aminothiophanthraquinone and 7.1 parts of the sodium salt of 1-meroapto-2-aminoanthraquinone by the method given in our co-pending application Serial No. 99,878, 9.5 parts of soda ash, 9.5 parts of potassium acetate, 0.28 part of cuprous chloride and 0.28 part of copper acetate was heated at 210215 C. for four hours. The charge was filtered at 100 C., and the cake was washed with nitrobenzene, alcohol, water and was dried. The yellow i, l-azobiphenyl- 4"-[5,6(N) thiophanthraquinone oxazole] 4"- [1,2(N) -anthraquinone thiazolel which was purified through acid pastin and bleaching, is represented by the formula:

It dyes vegetable fibers in bright red-yellow shades of excellent tinctorial strength from a red-orange alkaline hydrosulfite vat and gives an orange solution in concentrated sulfuric acid.

Example 4 '7 parts of 5,7-dibromo-6 aminothiophanthraquinone, and 6.8 parts of 1,3-dibromo-2-aminoanthraquinone by the method given in our pending application Serial No. 99,876] 9.8 parts of soda ash, 9.8 parts of potassium acetate, 0.3 partof ouprous chloride and 0.3 part of copper acetate was heated at reflux (210215 C.) for four hours. The charge was filtered at 80 C. and the cake Was washed with nitrobenzene, alcohol, water and was dried. The 4,4-azobipheny1-4"-[7 -bromo 5,6(N) thiophanthraquinone oxazole] -4" [3-bromo-1,2 (N) -anthraquinone oxazole], which was purified through acid pasting and bleaching, is represented by the formula:

It dyes vegetable fibers in yellow shades from an orange alkaline hydrosulfite vat and gives an orange solution in concentrated sulfuric acid.

Example 5 A mixture of 147 parts of dry nitrobenzene, 4,4 -azobiphenyl-4 -(6-carb0ny1amino-7-b1omothiophanthraquinone) -4 (2 carbonylamino- 3-bromoanthraquinone) [prepared from 7.5 parts of azobiphenylcarbonyl chloride, 5.3 parts of 6- amino 7 bromothiophanthraquinone and 5.2

parts of 2 amino 3 bromoanthraquinone as given in our co-pending application Serial No. 99,876], 8 parts of soda ash, 8 parts of potas- 5 sium acetate, 0.24 part of cuprous chloride and 0.24 part of copper acetate was heated at 210- 215 C. for four hours. The charge was filtered at 100 C., washed with nitrobenzene, alcohol, Water and was dried. The greenish-yellow 4,4-

0 azobiphenyll [6,7(N) thiophanthraquinone oxazolel-4' [2,3(N) anthraquinone oxazole] is represented by the formula:

To a mixture of 156 parts of dry ortho-dichlorobenzene and 13 parts of 4,4'-azobiphenyl 40 4" (6 carbonylaminothiophanthraquinone)- 4 2-carbonylaminoanthraquinone) was added 6.8 parts of phosphorous pentachloride at room temperature. The charge was heated at C. for five hours, at C. for one hour, and then filtered cold and the cake washed with ortho-dichlorobenzene, alcohol, ether and was dried. A mixture of 12 parts of the imide chloride described above, 96 parts of naphthalene and 12 parts of sulfur was refluxed at 215 C. about ten hours (until the fusion was completed) and the charge was cooled to 100 C., diluted with parts of xylene, and filtered cold. The cake was washed with xylene, alcohol, and water, and was dried. The yellow 4,4'-azobiphenyl-4"-[5,6(N) thiophanthraquinone thiazolell [1,2(N) anthraquinone thiazolel, which was purified through acid pasting and bleaching is represented by the formula:

fibers in red-yellow shades from It dyes vegetable an alkaline hydrosulfite vat and gives a yellow solution in concentrated sulfuric acid.

As illustrated in the above examples, the thicphanthraquinone azoles of this invention are readily prepared through routes normally used for the synthesis of azoles. Dioxazoles are prepared by treating a diorthohalogen diamide, preferably an alpha-diorthohalogen diamide with acid binding agents and copper catalysts as described above, Dioxazoles are also obtained by reacting a 4,4 -azobiphenyl-4 -carbonylaminothiophanthraquinone-e -carbonyl chloride containing halogen ortho to the amine with an orthoaminohydroxythiophanthraquinone or -anthraquinone to form a diimide which is ring closed first by heating with an acidic catalyst and then with acid binding agents and a copper catalyst. Oxazole-thiazoles result from reaction of the same acid chlorides with an ortho-mercaptoamino-thiophanthraquinone or -anthraquinone or with its sodium salt, ring closure being effected as described above.

Dithiazoles may be prepared by condensation of azobiphenyldicarbonyl chloride with orthomercaptoamino-thiophanthraquinones or- -anthraquinones or with the sodium salts, in the first case ring closure being effected by treatment with acidic agents, or in the latter case by heating. Dithiazoles may also be prepared by sulfur fusion of the diimide chlorides.

r-cop inc -co The condensations and azole ring closures may be carried out under a wide variety of conditions, depending upon the reactants employed. Temperatures in the range of 140-200 C. are usually used for most of the reactions, although temperatures outside of this range are occasionally necessary. The ring closures are carried out generally in the higher boiling inert organic solvents such as nitrobenzene, trichlorobenzene and naphthalene derivatives, in the presence of the usual catalysts necessary for the type reaction.

If desired, the reactions may be carried out without isolation of intermediate products, e. g., by condensing azobiphenyldicarbonyl chloride with a chloroor mercapto-aminoanthraquinone, then with a chloroaminoor mercaptoaminothiophanthraquinone followed by the usual ring closure.

The following valuable dyes may be prepared in the manner illustrated in the specific examples above, following the procedure illustrated for either the oxazoles, thiazoles or the mixed oxazole-thiazole compounds.

Li a:

oo -cor 75 and good printing properties.

2,559,678 9 10 We claim: and bromine, at least one R being a radical of 1. The azobiphenyldiazoles of the general forthe group consisting of thiophanthraquinone and mula: halogen-substituted thiophanthraquinone radiin which X stands for an element of the group cals, the thiophanthraquinone radicals in each consisting of Sulfur and oxygen and the HS stand case being connected to the azole ring through for radicals of the group consisting of thiophanb 1 thraquinone, anthraquinone and halogen-substi- 1 S enzene mm tuted thiophanthraquinone and halogen-substi- The p a ole 0f the formula:

oo en- 00o tuted anthroquinone radicals the halogen in each 3. The azobiphenyldiazole of the formula:

coo [in 033 t 45 case being of the group consisting of chlorine 4. The azobiphenyldiazole of the formula:

-io0- oo- 500 @3 t A HERMAN E. SCHROEDER. LORRAINE A. RINGROSE.

No references cited.

Certificate of Correction Patent No. 2,559,673 July 10, 1951 HERMAN E. SCHROEDER ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Columns 9 and 10, claim 1, for the formula reading read N and that the said Letters Patent should be read as corrected above, so that the same may conform to the record of the case in the Patent Ofiice.

Signed and sealed this 2nd day of October, A. D. 1951.

THOMAS MURPHY,

Assistant Commissioner of Patents. 

1. THE AZOBIPHENYLDIAZOLES OF THE GENERAL FORMULA: 